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Morphology, composition and electrochemistry of a nano-porous silicon versus bulk silicon anode for lithium-ion batteries

  • Batteries and Supercapacitors
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Abstract

The volumetric energy density of today’s lithium-ion batteries is limited mostly by the graphitic carbon anode. Silicon is a promising replacement but its excessive volume expansion on lithiation limits its long-term cyclability performance. A nano-sized aluminium containing silicon, leached in acid, with a porous structure is shown to maintain its capacity higher than pure bulk silicon or nano-sized silicon by over 700 mAh/g. The capacity of leached silicon is maintained at 1400 mAh/g for more than 60 cycles. X-ray diffraction, scanning electron microscopy, transmission electron microscopy and nuclear magnetic resonance spectroscopy have been used to correlate the electrochemical performance with the materials' morphology and composition.

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References

  1. Winter M, Brodd RJ (2004) What are batteries, fuel cells, and supercapacitors? Chem Rev 104:4245–4269

    Article  Google Scholar 

  2. Nesper R, Vonschnering HG (1987) Li2Si5, a zintl phase as well as a Hume-Rothery phase. J Solid State Chem 70:48–57

    Article  Google Scholar 

  3. Weydanz WJ, Wohlfahrt-Mehrens M, Huggins RA (1999) A room temperature study of the binary lithium–silicon and the ternary lithium–chromium–silicon system for use in rechargeable lithium batteries. J Power Sour 81:237–242

    Article  Google Scholar 

  4. Whittingham MS (2014) Ultimate limits to intercalation reactions for lithium batteries. Chem Rev 114:11414–11443

    Article  Google Scholar 

  5. Besenhard JO, Yang J, Winter M (1997) Will advanced lithium-alloy anodes have a chance in lithium-ion batteries? J Power Sour 68:87–90

    Article  Google Scholar 

  6. Winter M, Besenhard JO, Spahr ME, Novak P (1998) Insertion electrode materials for rechargeable lithium batteries. Adv Mater 10:725–763

    Article  Google Scholar 

  7. Yazami R, Genies S (1998) Chemical stability of lithiated-HOPG with some organic electrolytes. Denki Kagaku 66:1293–1298

    Google Scholar 

  8. Winter M, Besenhard JO (1999) Electrochemical lithiation of tin and tin-based intermetallics and composites. Electrochim Acta 45:31–50

    Article  Google Scholar 

  9. Baranchugov V, Markevich E, Pollak E, Salitra G, Aurbach D (2007) Amorphous silicon thin films as a high capacity anodes for Li-ion batteries in ionic liquid electrolytes. Electrochem Commun 9:796–800

    Article  Google Scholar 

  10. Xie C, Lin ZL, Hanson L, Cui Y, Cui BX (2012) Intracellular recording of action potentials by nanopillar electroporation. Nat Nanotechnol 7:185–190

    Article  Google Scholar 

  11. Li H, Huang XJ, Chen LQ, Wu ZG, Liang Y (1999) A high capacity nano-Si composite anode material for lithium rechargeable batteries. Electrochem Solid State Lett 2:547–549

    Article  Google Scholar 

  12. Yu Y, Gu L, Zhu C, Tsukimoto S, van Aken PA, Maier J (2010) Reversible storage of lithium in silver-coated three-dimensional macroporous silicon. Adv Mater 22(20):2247–2250

    Article  Google Scholar 

  13. Jia H, Gao P, Yang J, Wang J, Nuli Y, Yang Z (2011) Novel three-dimensional mesoporous silicon for high power lithium-ion battery anode material. Adv Energy Mater 1:1036–1039

    Article  Google Scholar 

  14. Yao Y, McDowell MT, Ryu I, Wu H, Liu N, Hu L, Nix WD, Cui Y (2011) Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life. Nano Lett 11:2949–2954

    Article  Google Scholar 

  15. Bogart TD, Chockla AM, Korgel BA (2013) High capacity lithium ion battery anodes of silicon and germanium. Curr Opin Chem Eng 2:286–293

    Article  Google Scholar 

  16. Szczech JR, Jin S (2011) Nanostructured silicon for high capacity lithium battery anodes. Energy Environ Sci 4:56–72

    Article  Google Scholar 

  17. Kohandehghan A, Kalisvaart P, Kupsta M, Zahiri B, Amirkhiz BS, Li ZP, Memarzadeh EL, Bendersky LA, Mitlin D (2013) Magnesium and magnesium-silicide coated silicon nanowire composite anodes for lithium-ion batteries. J Mater Chem A 1:1600–1612

    Article  Google Scholar 

  18. Kohandehghan A, Cui K, Kupsta M, Memarzadeh E, Kalisvaart P, Mitlin D (2014) Nanometer-scale Sn coatings improve the performance of silicon nanowire LIB anodes. J Mater Chem A 2:11261–11279

    Article  Google Scholar 

  19. Sayama HYK, Kato Y, Matsuta S, Tarui H, Fujitani S (2002) In: Abstract 52, the 11th international meeting on lithium batteries, Monterey, CA

  20. Takamura SOT, Suzuki J, Sekine K (2002) In: Abstract 257, the 11th international meeting on lithium batteries, Monterey, CA

  21. Park MH, Kim MG, Joo J, Kim K, Kim J, Ahn S, Cui Y, Cho J (2009) Silicon nanotube battery anodes. Nano Lett 9:3844–3847

    Article  Google Scholar 

  22. Lotfabad EM, Kalisvaart P, Kohandehghan A, Cui K, Kupsta M, Farbod B, Mitlin D (2014) Si nanotubes ALD coated with TiO2, TiN or Al2O3 as high performance lithium ion battery anodes. J Mater Chem A 2:2504–2516

    Article  Google Scholar 

  23. Chan CK, Peng H, Liu G, McIlwrath K, Zhang XF, Huggins RA, Cui Y (2008) High-performance lithium battery anodes using silicon nanowires. Nat Nanotechnol 3:31–35

    Article  Google Scholar 

  24. Wang CS, Wu GT, Zhang XB, Qi ZF, Li WZ (1998) Lithium insertion in carbon-silicon composite materials produced by mechanical milling. J Electrochem Soc 145:2751–2758

    Article  Google Scholar 

  25. Kim I, Kumta PN, Blomgren GE (2000) Si/TiN nanocomposites-novel anode materials for Li-ion batteries. Electrochem Solid State Lett 3:493–496

    Article  Google Scholar 

  26. Graetz J, Ahn CC, Yazami R, Fultz B (2003) Highly reversible lithium storage in nanostructured silicon. Electrochem Solid State Lett 6:A194–A197

    Article  Google Scholar 

  27. Hwang G, Park H, Bok T, Choi S, Lee S, Hwang I, Choi NS, Seo K, Park S (2015) A high-performance nanoporous Si/Al2O3 foam lithium-ion battery anode fabricated by selective chemical etching of the Al–Si alloy and subsequent thermal oxidation. Chem Commun 51:4429–4432

    Article  Google Scholar 

  28. Zhou W, Jiang T, Zhou H, Wang Y, Fang J, Whittingham MS (2013) The nanostructure of the Si–Al eutectic and its use in lithium batteries. MRS Commun 3:119–121

    Article  Google Scholar 

  29. Murray AMJ (1984) The Al–Si (aluminum–silicon) system. J Phase Equilib 5:74–84

    Google Scholar 

  30. Larson AC, Von Dreele RB (2000) General structure analysis system (GSAS). Los Alamos National Laboratory report. LAUR 86-748, Los Alamos National Laboratory, Los Alamo

  31. Toby BH (2001) EXPGUI, a graphical user interface for GSAS. J Appl Crystallogr 34:210–213

    Article  Google Scholar 

  32. Kasavajjula U, Wang C, Appleby AJ (2007) Nano- and bulk-silicon-based insertion anodes for lithium-ion secondary cells. J Power Sour 163:1003–1039

    Article  Google Scholar 

  33. Lee YM, Lee JY, Shim H-T, Lee JK, Park J-K (2007) SEI layer formation on amorphous Si thin electrode during precycling. J Electrochem Soc 154:A515–A519

    Article  Google Scholar 

  34. Hull R (1999) Properties of crystalline silicon. IET, London

    Google Scholar 

  35. Jeong G, Kim Y-U, Krachkovskiy SA, Lee CK (2010) A nanostructured SiAl0.2O anode material for lithium batteries. Chem Mater 22:5570–5579

    Article  Google Scholar 

  36. Hohl A, Wieder T, van Aken PA, Weirich TE, Denninger G, Vidal M, Oswald S, Deneke C, Mayer J, Fuess H (2003) An interface clusters mixture model for the structure of amorphous silicon monoxide (SiO). J Non-Cryst Solids 320:255–280

    Article  Google Scholar 

Download references

Acknowledgements

This research is based upon work supported by DOE-EERE, as part of BATT, DE-AC02-05CH11231 under Award Number 6807148. Use of the National Synchrotron Light Source at Brookhaven National Laboratory is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-98CH10886. We thank Dr. Shailesh Upreti for providing the milled silicon sample. We also thank Qiyue Yin from Prof. Guangwen Zhou’s group for her help with TEM analysis, which was carried out in part at the Center for Functional Nanomaterials, Brookhaven National Laboratory, and supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-SC0012704. And we thank Dr. Juergen T. Schulte and Jordi Cabana for their help with the NMR analysis.

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Authors and Affiliations

  1. Institute for Materials Research and Department of Chemistry, State University of New York at Binghamton, Binghamton, NY, USA

    Tianchan Jiang, Ruibo Zhang, Qiyue Yin, Wenchao Zhou, Zhixin Dong, Natasha A. Chernova, Qi Wang, Fredrick Omenya & M. Stanley Whittingham

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  1. Tianchan Jiang
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  2. Ruibo Zhang
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  3. Qiyue Yin
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  4. Wenchao Zhou
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  7. Qi Wang
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  9. M. Stanley Whittingham
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Correspondence to Tianchan Jiang.

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Jiang, T., Zhang, R., Yin, Q. et al. Morphology, composition and electrochemistry of a nano-porous silicon versus bulk silicon anode for lithium-ion batteries. J Mater Sci 52, 3670–3677 (2017). https://doi.org/10.1007/s10853-016-0599-8

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  • DOI: https://doi.org/10.1007/s10853-016-0599-8

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